CN118702882A - Preparation method of modified phenolic resin - Google Patents
Preparation method of modified phenolic resin Download PDFInfo
- Publication number
- CN118702882A CN118702882A CN202410823467.XA CN202410823467A CN118702882A CN 118702882 A CN118702882 A CN 118702882A CN 202410823467 A CN202410823467 A CN 202410823467A CN 118702882 A CN118702882 A CN 118702882A
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- heating
- stirring
- reaction
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 200
- 238000006243 chemical reaction Methods 0.000 claims abstract description 115
- 238000003756 stirring Methods 0.000 claims abstract description 104
- 238000010438 heat treatment Methods 0.000 claims abstract description 85
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000007864 aqueous solution Substances 0.000 claims abstract description 49
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 45
- 239000005011 phenolic resin Substances 0.000 claims abstract description 45
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001816 cooling Methods 0.000 claims abstract description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 32
- 239000011574 phosphorus Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 24
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 22
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 22
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000018044 dehydration Effects 0.000 claims abstract description 18
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 18
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 18
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 14
- -1 phosphorus modified phenolic resin Chemical class 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 description 19
- 238000012986 modification Methods 0.000 description 19
- 229910052796 boron Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 6
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 244000226021 Anacardium occidentale Species 0.000 description 3
- 235000020226 cashew nut Nutrition 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a preparation method of modified phenolic resin, which comprises the steps of firstly heating phenol and cardanol to be molten respectively and mixing to obtain mixed phenol, then adding nitrile rubber and p-toluenesulfonic acid into the mixed phenol, carrying out first heating and stirring reaction, naturally cooling, slowly dropwise adding a first part of formaldehyde aqueous solution, stirring and mixing uniformly, carrying out second heating and stirring reaction, and carrying out first vacuumizing and dehydration; naturally cooling, adding a phosphorus-containing organic compound and a second part of formaldehyde aqueous solution, heating and stirring for the third time for reaction under inert atmosphere, and vacuumizing and dehydrating for the second time to obtain phosphorus-modified phenolic resin; and then, ultrasonically dispersing the phosphorus modified phenolic resin in absolute ethyl alcohol to obtain phenolic resin dispersion liquid, then slowly adding titanate acetylacetone mixed liquid into the phenolic resin dispersion liquid, stirring for reaction, concentrating under reduced pressure, and cooling to obtain the phenolic resin. The modified phenolic resin obtained by the invention has excellent heat resistance and good toughness.
Description
Technical Field
The invention relates to a preparation method of modified phenolic resin. Belongs to the technical field of phenolic resin preparation.
Background
Phenolic resin is a synthetic resin with wide application, low cost, good heat resistance, high mechanical strength, stable performance and the like. The phenolic resin is suitable for preparing glass fiber reinforced plastic, molding compound, paint, adhesive, fireproof material binding agent, heat insulating material, etc. However, the cured phenolic resin is connected with each other only by methylene, so that the molecular chain has poor flexibility and high brittleness, and the prepared phenolic foam has small toughness, high powder dropping rate and the like, thereby influencing the popularization and application of the phenolic resin. Therefore, the toughening modification research of the phenolic resin is very necessary.
Although phenolic resins have relatively good heat resistance, phenolic hydroxyl groups and methylene groups of phenolic resins are easily oxidized, the heat resistance is affected, the thermal decomposition phenomenon of ordinary phenolic resins is quite serious at temperatures exceeding 300 ℃, and the carbon residue rate is only about 40% at high temperatures (above 800 ℃). In recent years, with the continuous development of industry, particularly the fields of automobiles, electronics, aviation, aerospace and the like, the requirements on materials are higher, so that further heat-resistant modification of phenolic resin is of great importance.
The phenolic resin is toughened and modified by the following method:
1. adding an external toughening agent, and realizing toughening in a blending mode;
2. the aim of toughening is achieved through the chemical reaction of the resole resin and the toughening agent;
3. phenol is replaced by modified phenol with part of toughness chain to synthesize phenolic resin.
For heat resistance modification, one is mainly realized by the following method:
1. Inorganic nano particles or compounds containing inorganic elements, such as boron, molybdenum, silicon, phosphorus, zirconium, titanium and the like, with good oxidation resistance are introduced;
2. Structures with higher thermal stability, such as imide groups, triazine rings, polysulfone and the like are introduced.
At present, people usually carry out single toughening modification or single heat-resistant modification, if the toughening and heat resistance are to be realized simultaneously, the steps are often complicated, and the effect of the final product is not ideal.
Patent application CN116217846a discloses a method for synthesizing catalyst-free boron modified phenolic resin, firstly, phenol and boric acid are heated for reaction, after reaction water is removed, cooling is carried out, paraformaldehyde is added, heating and stirring reaction are carried out, reaction water is removed while reaction is carried out under vacuum condition, cooling is carried out, and boron modified phenolic resin is obtained. The technology of the patent is mainly improved in that the catalyst-free preparation is realized, and the heat resistance and mechanical properties of the product are improved through boron modification. The B-O bond energy formed by replacing hydrogen in the phenolic hydroxyl group with boron is far greater than the C-C bond energy, and the boron carbide honeycomb structure formed on the surface of the resin during high-temperature pyrolysis can prevent heat from diffusing inwards to protect the internal structure, so that the boron modified phenolic resin has excellent heat resistance. However, the boron modified phenolic resin obtained by the technology has poor storage stability, is easy to separate out boric acid or agglomerate, and in addition, B-O bonds are easy to hydrolyze, so that the water resistance of the resin is poor.
Patent application CN107082859A discloses a preparation method of toughened heat-resistant modified phenolic resin, which comprises the steps of heating, mixing and reacting phenol, a modifier and a composite acid catalyst, cooling, dripping aldehyde, heating and reacting, devolatilizing, adding boric acid, heating and reacting, and devolatilizing. The phenolic resin has the advantages that through double modification of cardanol/boric acid or cashew nut shell oil/boric acid, the toughness of the phenolic resin is improved, and meanwhile, the problem that the heat resistance of the phenolic resin is reduced due to the introduction of cardanol or cashew nut shell oil is also modified. The boron modification in this patent application also has the aforementioned problems, even because the modification of cardanol/cashew nut shell oil followed by boron modification affects the effect of boron modification, and the improvement degree of the product performance is worse than that of patent application CN116217846 a.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of modified phenolic resin.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The preparation method of the modified phenolic resin comprises the following specific steps:
(1) Firstly, respectively heating phenol and cardanol to be molten and mixing to obtain mixed phenol, then adding nitrile rubber and p-toluenesulfonic acid into the mixed phenol, carrying out first heating and stirring reaction, naturally cooling, slowly dripping a first part of formaldehyde aqueous solution, stirring and uniformly mixing, carrying out second heating and stirring reaction, and carrying out first vacuumizing and dewatering;
(2) Naturally cooling, adding a phosphorus-containing organic compound and a second part of formaldehyde aqueous solution, heating and stirring for the third time for reaction under inert atmosphere, and vacuumizing and dehydrating for the second time to obtain phosphorus-modified phenolic resin;
(3) And then, ultrasonically dispersing the phosphorus modified phenolic resin in absolute ethyl alcohol to obtain phenolic resin dispersion liquid, then, slowly adding titanate acetylacetone mixed liquid into the phenolic resin dispersion liquid, stirring for reaction, concentrating under reduced pressure, and cooling to obtain the modified phenolic resin.
Preferably, in the steps (1) and (2), the molar ratio of phenol, cardanol, formaldehyde contained in the first part of formaldehyde aqueous solution, the phosphorus-containing organic compound, and formaldehyde contained in the second part of formaldehyde aqueous solution is 1:0.1 to 0.2:0.7 to 0.9:0.2 to 0.3:0.3 to 0.4 percent, and the mass concentration of the formaldehyde aqueous solution is 37 percent.
Further preferably, the phosphorus-containing organic compound is triphenyl phosphate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in a molar ratio of 0.3:0.1 to 0.2.
Preferably, in the step (1), the mass ratio of phenol, nitrile rubber and p-toluenesulfonic acid is 1:0.02 to 0.03:0.0002 to 0.0003.
Preferably, in the step (1), the process conditions of the first heating and stirring reaction are as follows: stirring and reacting for 1-2 hours at the temperature of 120-130 ℃ at the speed of 300-400 r/min.
Preferably, in the step (1), the mixture is naturally cooled to the temperature of the second heating and stirring reaction, and under the condition of heat preservation, the first part of formaldehyde aqueous solution is slowly and uniformly dripped for 40-50 minutes.
Preferably, in the step (1), the process conditions of the second heating and stirring reaction are as follows: stirring and reacting for 3-4 hours at the temperature of 95-105 ℃ and the speed of 300-400 r/min.
Preferably, in the step (1), the technological conditions of the first vacuumizing and dehydrating are as follows: the temperature is 90-100 ℃, the vacuum degree is 8-10 kPa, and the time is 50-60 minutes.
Preferably, in the step (2), the reaction mixture is naturally cooled to the temperature of the third heating and stirring reaction.
Preferably, in the step (2), the process conditions of the third heating and stirring reaction are as follows: stirring and reacting for 90-100 minutes at the temperature of 70-80 ℃ at the speed of 300-400 r/min.
Preferably, in the step (2), the technological conditions of the second vacuumizing and dehydrating are as follows: the temperature is 80-90 ℃, the vacuum degree is 5-8 kPa, and the time is 100-120 minutes.
Preferably, in the step (3), the mass ratio of the phosphorus modified phenolic resin, the absolute ethyl alcohol and the titanate acetylacetone mixed solution is 2.5-3.5: 2:1.5 to 2, wherein the titanate and acetylacetone mixed solution is prepared by mixing titanate and acetylacetone according to a mass ratio of 1: 10.
Further preferably, the titanate is selected from isopropyl titanate or n-butyl titanate.
Preferably, in the step (3), the titanate acetylacetone mixed solution is slowly and uniformly added into the phenolic resin dispersion liquid by 30-40 minutes.
Preferably, in the step (3), the process conditions of the stirring reaction are as follows: stirring and reacting for 50-60 minutes at the temperature of 25-30 ℃ and the speed of 200-300 r/min.
Preferably, in the step (3), the process conditions of the reduced pressure concentration are as follows: the temperature is 70-75 ℃, the vacuum degree is 5-8 kPa, and the time is 80-100 minutes.
The invention has the beneficial effects that:
Firstly, respectively heating phenol and cardanol to be molten and mixing to obtain mixed phenol, then adding nitrile rubber and p-toluenesulfonic acid into the mixed phenol, carrying out first heating and stirring reaction, naturally cooling, slowly dropwise adding a first part of formaldehyde aqueous solution, stirring and uniformly mixing, carrying out second heating and stirring reaction, and carrying out first vacuumizing and dehydration; naturally cooling, adding a phosphorus-containing organic compound and a second part of formaldehyde aqueous solution, heating and stirring for the third time for reaction under inert atmosphere, and vacuumizing and dehydrating for the second time to obtain phosphorus-modified phenolic resin; and then, ultrasonically dispersing the phosphorus modified phenolic resin in absolute ethyl alcohol to obtain phenolic resin dispersion liquid, then, slowly adding titanate acetylacetone mixed liquid into the phenolic resin dispersion liquid, stirring for reaction, concentrating under reduced pressure, and cooling to obtain the modified phenolic resin. The modified phenolic resin obtained by the invention has excellent heat resistance and good toughness.
According to the invention, part of phenol is replaced by cardanol, and compared with phenol, the heat resistance and toughness of the obtained product are obviously improved.
The formaldehyde aqueous solution is added twice, so that the reaction is more complete, the raw materials are saved, the yield is improved, and the production is more environment-friendly.
The nitrile rubber is added when the mixed phenol reacts with the first part of formaldehyde aqueous solution, the mixed phenol reacts with the nitrile rubber in an addition way, and the mixed phenol further reacts with formaldehyde, so that the rubber graft modification of the phenolic resin is realized, and the heat resistance and toughness of the product are further improved.
The invention introduces phosphorus by using the phosphorus-containing organic compound, is more stable in the system, can be cooperated with other components, and further improves the heat resistance and toughness of the product.
Finally, the invention utilizes titanate to carry out titanium modification on the phenolic resin, and other components act synergistically to further improve the heat resistance and toughness of the product.
Detailed Description
The present invention will be further illustrated by the following examples, which are given by way of illustration only and are not intended to be limiting.
Example 1:
The preparation method of the modified phenolic resin comprises the following specific steps:
(1) Firstly, respectively heating 5kg of phenol and cardanol to be molten and mixing to obtain mixed phenol, then adding 0.1kg of nitrile rubber and 1g of p-toluenesulfonic acid into the mixed phenol, carrying out primary heating and stirring reaction, naturally cooling, slowly dropwise adding a first part of formaldehyde aqueous solution, stirring and uniformly mixing, carrying out secondary heating and stirring reaction, and carrying out primary vacuumizing and dewatering;
(2) Naturally cooling, adding a phosphorus-containing organic compound and a second part of formaldehyde aqueous solution, heating and stirring for the third time for reaction under inert atmosphere, and vacuumizing and dehydrating for the second time to obtain phosphorus-modified phenolic resin;
(3) Then dispersing 2.5kg of phosphorus modified phenolic resin in 2kg of absolute ethyl alcohol in an ultrasonic manner to obtain phenolic resin dispersion liquid, then slowly adding 1.5kg of titanate acetylacetone mixed liquid (obtained by mixing titanate and acetylacetone according to the mass ratio of 1:10) into the phenolic resin dispersion liquid, stirring for reaction, concentrating under reduced pressure, and cooling to obtain the modified phenolic resin.
In the steps (1) and (2), the mole ratio of the formaldehyde contained in the phenol, cardanol and the first part of formaldehyde aqueous solution to the formaldehyde contained in the second part of formaldehyde aqueous solution is 1:0.1:0.7:0.2:0.3, the mass concentration of the formaldehyde aqueous solution is 37%.
The phosphorus-containing organic compound is triphenyl phosphate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the molar ratio is 0.3: 0.1.
In the step (1), the process conditions of the first heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 1 hour at 120 ℃.
Naturally cooling to the temperature of the second heating and stirring reaction, and slowly and uniformly dropwise adding the first part of formaldehyde aqueous solution under the condition of heat preservation by 40 minutes.
The process conditions of the second heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 3 hours at 95 ℃.
The technological conditions of the first vacuumizing dehydration are as follows: the temperature was 90℃and the vacuum was 8kPa for 50 minutes.
In the step (2), naturally cooling to the temperature of the third heating and stirring reaction.
The process conditions of the third heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 90 minutes at 70 ℃.
The technological conditions of the second vacuumizing dehydration are as follows: the temperature is 80 ℃, the vacuum degree is 5kPa, and the time is 100 minutes.
In the step (3), the titanate is isopropyl titanate.
The titanate acetylacetonate mixture was slowly added to the phenolic resin dispersion at a constant rate over 30 minutes.
The technological conditions of the stirring reaction are as follows: the reaction was stirred at 200r/min for 50 minutes at 25 ℃.
The process conditions of the reduced pressure concentration are as follows: the temperature was 70℃and the vacuum was 5kPa for 80 minutes.
Example 2:
The preparation method of the modified phenolic resin comprises the following specific steps:
(1) Firstly, respectively heating 5kg of phenol and cardanol to be molten and mixing to obtain mixed phenol, then adding 0.15kg of nitrile rubber and 1.5g of p-toluenesulfonic acid into the mixed phenol, carrying out primary heating and stirring reaction, naturally cooling, slowly dropwise adding a first part of formaldehyde aqueous solution, stirring and uniformly mixing, carrying out secondary heating and stirring reaction, and carrying out primary vacuumizing and dehydration;
(2) Naturally cooling, adding a phosphorus-containing organic compound and a second part of formaldehyde aqueous solution, heating and stirring for the third time for reaction under inert atmosphere, and vacuumizing and dehydrating for the second time to obtain phosphorus-modified phenolic resin;
(3) Then 3.5kg of phosphorus modified phenolic resin is ultrasonically dispersed in 2kg of absolute ethyl alcohol to obtain phenolic resin dispersion liquid, then 2kg of titanate acetylacetone mixed liquid (the mixture of titanate and acetylacetone is obtained according to the mass ratio of 1:10) is slowly added into the phenolic resin dispersion liquid, stirred for reaction, decompressed for concentration and cooled to obtain the modified phenolic resin.
In the steps (1) and (2), the mole ratio of the formaldehyde contained in the phenol, cardanol and the first part of formaldehyde aqueous solution to the formaldehyde contained in the second part of formaldehyde aqueous solution is 1:0.2:0.9:0.3:0.4, the mass concentration of the aqueous formaldehyde solution is 37%.
The phosphorus-containing organic compound is triphenyl phosphate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the molar ratio is 0.3: 0.2.
In the step (1), the process conditions of the first heating and stirring reaction are as follows: the reaction was stirred at 130℃for 2 hours at 400 r/min.
Naturally cooling to the temperature of the second heating and stirring reaction, and slowly and uniformly dropwise adding the first part of formaldehyde aqueous solution under the condition of heat preservation for 50 minutes.
The process conditions of the second heating and stirring reaction are as follows: the reaction was stirred at 400r/min for 4 hours at 105 ℃.
The technological conditions of the first vacuumizing dehydration are as follows: the temperature is 100 ℃, the vacuum degree is 10kPa, and the time is 60 minutes.
In the step (2), naturally cooling to the temperature of the third heating and stirring reaction.
The process conditions of the third heating and stirring reaction are as follows: the reaction was stirred at 400r/min for 100 minutes at 80 ℃.
The technological conditions of the second vacuumizing dehydration are as follows: the temperature was 90℃and the vacuum was 8kPa for 120 minutes.
In the step (3), the titanate is n-butyl titanate.
The titanate acetylacetonate mixture was slowly added to the phenolic resin dispersion at a constant rate over 40 minutes.
The technological conditions of the stirring reaction are as follows: the reaction was stirred at 300r/min for 60 minutes at 30 ℃.
The process conditions of the reduced pressure concentration are as follows: the temperature was 75℃and the vacuum was 8kPa for 100 minutes.
Example 3:
The preparation method of the modified phenolic resin comprises the following specific steps:
(1) Firstly, respectively heating 5kg of phenol and cardanol to be molten and mixing to obtain mixed phenol, then adding 0.1kg of nitrile rubber and 1.5g of p-toluenesulfonic acid into the mixed phenol, carrying out primary heating and stirring reaction, naturally cooling, slowly dropwise adding a first part of formaldehyde aqueous solution, stirring and uniformly mixing, carrying out secondary heating and stirring reaction, and carrying out primary vacuumizing and dehydration;
(2) Naturally cooling, adding a phosphorus-containing organic compound and a second part of formaldehyde aqueous solution, heating and stirring for the third time for reaction under inert atmosphere, and vacuumizing and dehydrating for the second time to obtain phosphorus-modified phenolic resin;
(3) Then dispersing 2.5kg of phosphorus modified phenolic resin in 2kg of absolute ethyl alcohol in an ultrasonic manner to obtain phenolic resin dispersion liquid, then slowly adding 2kg of titanate acetylacetone mixed liquid (obtained by mixing titanate and acetylacetone according to the mass ratio of 1:10) into the phenolic resin dispersion liquid, stirring for reaction, concentrating under reduced pressure, and cooling to obtain the modified phenolic resin.
In the steps (1) and (2), the mole ratio of the formaldehyde contained in the phenol, cardanol and the first part of formaldehyde aqueous solution to the formaldehyde contained in the second part of formaldehyde aqueous solution is 1:0.1:0.9:0.2:0.4, the mass concentration of the aqueous formaldehyde solution is 37%.
The phosphorus-containing organic compound is triphenyl phosphate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the molar ratio is 0.3: 0.1.
In the step (1), the process conditions of the first heating and stirring reaction are as follows: the reaction was stirred at 130℃for 2 hours at 300 r/min.
Naturally cooling to the temperature of the second heating and stirring reaction, and slowly and uniformly dropwise adding the first part of formaldehyde aqueous solution under the condition of heat preservation by 40 minutes.
The process conditions of the second heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 4 hours at 105 ℃.
The technological conditions of the first vacuumizing dehydration are as follows: the temperature is 90 ℃, the vacuum degree is 10kPa, and the time is 50 minutes.
In the step (2), naturally cooling to the temperature of the third heating and stirring reaction.
The process conditions of the third heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 100 minutes at 80 ℃.
The technological conditions of the second vacuumizing dehydration are as follows: the temperature was 80℃and the vacuum was 8kPa for 100 minutes.
In the step (3), the titanate is isopropyl titanate.
The titanate acetylacetonate mixture was slowly added to the phenolic resin dispersion at a constant rate over 40 minutes.
The technological conditions of the stirring reaction are as follows: the reaction was stirred at 300r/min for 50 minutes at 25 ℃.
The process conditions of the reduced pressure concentration are as follows: the temperature was 75℃and the vacuum was 5kPa for 100 minutes.
Example 4:
The preparation method of the modified phenolic resin comprises the following specific steps:
(1) Firstly, respectively heating 5kg of phenol and cardanol to be molten and mixing to obtain mixed phenol, then adding 0.12kg of nitrile rubber and 1.2g of p-toluenesulfonic acid into the mixed phenol, carrying out primary heating and stirring reaction, naturally cooling, slowly dropwise adding a first part of formaldehyde aqueous solution, stirring and uniformly mixing, carrying out secondary heating and stirring reaction, and carrying out primary vacuumizing and dehydration;
(2) Naturally cooling, adding a phosphorus-containing organic compound and a second part of formaldehyde aqueous solution, heating and stirring for the third time for reaction under inert atmosphere, and vacuumizing and dehydrating for the second time to obtain phosphorus-modified phenolic resin;
(3) Then 3kg of phosphorus modified phenolic resin is ultrasonically dispersed in 2kg of absolute ethyl alcohol to obtain phenolic resin dispersion liquid, then 1.8kg of titanate acetylacetone mixed liquid (obtained by mixing titanate and acetylacetone according to the mass ratio of 1:10) is slowly added into the phenolic resin dispersion liquid, stirred for reaction, decompressed for concentration and cooled to obtain the modified phenolic resin.
In the steps (1) and (2), the mole ratio of the formaldehyde contained in the phenol, cardanol and the first part of formaldehyde aqueous solution to the formaldehyde contained in the second part of formaldehyde aqueous solution is 1:0.15:0.8:0.25:0.35, and the mass concentration of the formaldehyde aqueous solution is 37%.
The phosphorus-containing organic compound is triphenyl phosphate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the molar ratio is 0.3: 0.15.
In the step (1), the process conditions of the first heating and stirring reaction are as follows: stirring at 125 deg.c and 400r/min for reaction for 1-2 hr.
Naturally cooling to the temperature of the second heating and stirring reaction, and slowly and uniformly dropwise adding the first part of formaldehyde aqueous solution in 45 minutes under the condition of heat preservation.
The process conditions of the second heating and stirring reaction are as follows: the reaction was stirred at 400r/min for 3.5 hours at 100 ℃.
The technological conditions of the first vacuumizing dehydration are as follows: the temperature was 95℃and the vacuum was 9kPa for 55 minutes.
In the step (2), naturally cooling to the temperature of the third heating and stirring reaction.
The process conditions of the third heating and stirring reaction are as follows: the reaction was stirred at 400r/min for 95 min at 75 ℃.
The technological conditions of the second vacuumizing dehydration are as follows: the temperature was 85℃and the vacuum was 6kPa for 110 minutes.
In the step (3), the titanate is n-butyl titanate.
The titanate acetylacetonate mixture was slowly added to the phenolic resin dispersion at a constant rate over 35 minutes.
The technological conditions of the stirring reaction are as follows: the reaction was stirred at 300r/min for 55 minutes at 27 ℃.
The process conditions of the reduced pressure concentration are as follows: the temperature was 72℃and the vacuum was 6kPa for 90 minutes.
Comparative example 1
The preparation method of the modified phenolic resin comprises the following specific steps:
(1) Firstly, respectively heating 5kg of phenol and cardanol to be molten and mixing to obtain mixed phenol, then adding 0.1kg of nitrile rubber and 1g of p-toluenesulfonic acid into the mixed phenol, carrying out primary heating and stirring reaction, naturally cooling, slowly dropwise adding a first part of formaldehyde aqueous solution, stirring and uniformly mixing, carrying out secondary heating and stirring reaction, and carrying out primary vacuumizing and dewatering;
(2) Naturally cooling, adding a second part of formaldehyde aqueous solution, heating and stirring for reacting for the third time under inert atmosphere, and vacuumizing and dehydrating for the second time to obtain the pre-modified phenolic resin;
(3) Then dispersing 2.5kg of pre-modified phenolic resin in 2kg of absolute ethyl alcohol in an ultrasonic manner to obtain phenolic resin dispersion liquid, then slowly adding 1.5kg of titanate acetylacetone mixed liquid (obtained by mixing titanate and acetylacetone according to the mass ratio of 1:10) into the phenolic resin dispersion liquid, stirring for reaction, concentrating under reduced pressure, and cooling to obtain the modified phenolic resin.
In the steps (1) and (2), the molar ratio of phenol, cardanol, formaldehyde contained in the first part of formaldehyde aqueous solution to formaldehyde contained in the second part of formaldehyde aqueous solution is 1:0.1:0.7:0.3, the mass concentration of the formaldehyde aqueous solution is 37%.
In the step (1), the process conditions of the first heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 1 hour at 120 ℃.
Naturally cooling to the temperature of the second heating and stirring reaction, and slowly and uniformly dropwise adding the first part of formaldehyde aqueous solution under the condition of heat preservation by 40 minutes.
The process conditions of the second heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 3 hours at 95 ℃.
The technological conditions of the first vacuumizing dehydration are as follows: the temperature was 90℃and the vacuum was 8kPa for 50 minutes.
In the step (2), naturally cooling to the temperature of the third heating and stirring reaction.
The process conditions of the third heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 90 minutes at 70 ℃.
The technological conditions of the second vacuumizing dehydration are as follows: the temperature is 80 ℃, the vacuum degree is 5kPa, and the time is 100 minutes.
In the step (3), the titanate is isopropyl titanate.
The titanate acetylacetonate mixture was slowly added to the phenolic resin dispersion at a constant rate over 30 minutes.
The technological conditions of the stirring reaction are as follows: the reaction was stirred at 200r/min for 50 minutes at 25 ℃.
The process conditions of the reduced pressure concentration are as follows: the temperature was 70℃and the vacuum was 5kPa for 80 minutes.
Comparative example 2
The preparation method of the modified phenolic resin comprises the following specific steps:
(1) Firstly, respectively heating 5kg of phenol and cardanol to be molten and mixing to obtain mixed phenol, then adding 0.1kg of nitrile rubber and 1g of p-toluenesulfonic acid into the mixed phenol, carrying out primary heating and stirring reaction, naturally cooling, slowly dropwise adding a first part of formaldehyde aqueous solution, stirring and uniformly mixing, carrying out secondary heating and stirring reaction, and carrying out primary vacuumizing and dewatering;
(2) Naturally cooling, adding a phosphorus-containing organic compound and a second part of formaldehyde aqueous solution, heating and stirring for a third time for reaction under inert atmosphere, and vacuumizing and dehydrating for a second time to obtain the modified phenolic resin.
In the steps (1) and (2), the mole ratio of the formaldehyde contained in the phenol, cardanol and the first part of formaldehyde aqueous solution to the formaldehyde contained in the second part of formaldehyde aqueous solution is 1:0.1:0.7:0.2:0.3, the mass concentration of the formaldehyde aqueous solution is 37%.
The phosphorus-containing organic compound is triphenyl phosphate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the molar ratio is 0.3: 0.1.
In the step (1), the process conditions of the first heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 1 hour at 120 ℃.
Naturally cooling to the temperature of the second heating and stirring reaction, and slowly and uniformly dropwise adding the first part of formaldehyde aqueous solution under the condition of heat preservation by 40 minutes.
The process conditions of the second heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 3 hours at 95 ℃.
The technological conditions of the first vacuumizing dehydration are as follows: the temperature was 90℃and the vacuum was 8kPa for 50 minutes.
In the step (2), naturally cooling to the temperature of the third heating and stirring reaction.
The process conditions of the third heating and stirring reaction are as follows: the reaction was stirred at 300r/min for 90 minutes at 70 ℃.
The technological conditions of the second vacuumizing dehydration are as follows: the temperature is 80 ℃, the vacuum degree is 5kPa, and the time is 100 minutes.
Test examples
The modified phenolic resins obtained in examples 1 to 4 and comparative examples 1 and 2 were examined for their properties.
The modified phenolic resin was prepared into a sample having a size of 15 cm. Times.3 cm, and the impact strength of the modified phenolic resin was tested with reference to GB/T1451-2005.
And (3) performing thermal weight loss test under the conditions of 30-800 ℃ and heating rate of 10 ℃/min to obtain the quality retention rate at 800 ℃.
The results are shown in Table 1.
TABLE 1 test results
| Impact strength (MPa) | Mass retention at 800 ℃ (%) | |
| Example 1 | 42.3 | 90.1 |
| Example 2 | 42.5 | 90.1 |
| Example 3 | 43.1 | 90.6 |
| Example 4 | 43.8 | 91.8 |
| Comparative example 1 | 35.6 | 80.7 |
| Comparative example 2 | 32.2 | 83.4 |
As is clear from Table 1, the modified phenolic resins obtained in examples 1 to 4 were excellent in heat resistance and toughness.
Comparative example 1 omits phosphorus modification, comparative example 2 omits titanium modification, and heat resistance and toughness are both obviously deteriorated, which shows that the heat resistance and toughness of the product are improved through the synergistic effect of rubber modification, phosphorus modification and titanium modification.
While the foregoing describes the embodiments of the present invention, it is not intended to limit the scope of the present invention, and various modifications or variations may be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the modified phenolic resin is characterized by comprising the following specific steps:
(1) Firstly, respectively heating phenol and cardanol to be molten and mixing to obtain mixed phenol, then adding nitrile rubber and p-toluenesulfonic acid into the mixed phenol, carrying out first heating and stirring reaction, naturally cooling, slowly dripping a first part of formaldehyde aqueous solution, stirring and uniformly mixing, carrying out second heating and stirring reaction, and carrying out first vacuumizing and dewatering;
(2) Naturally cooling, adding a phosphorus-containing organic compound and a second part of formaldehyde aqueous solution, heating and stirring for the third time for reaction under inert atmosphere, and vacuumizing and dehydrating for the second time to obtain phosphorus-modified phenolic resin;
(3) And then, ultrasonically dispersing the phosphorus modified phenolic resin in absolute ethyl alcohol to obtain phenolic resin dispersion liquid, then, slowly adding titanate acetylacetone mixed liquid into the phenolic resin dispersion liquid, stirring for reaction, concentrating under reduced pressure, and cooling to obtain the modified phenolic resin.
2. The method according to claim 1, wherein in the steps (1) and (2), the molar ratio of formaldehyde contained in the phenol, cardanol, the first part of aqueous formaldehyde solution, the phosphorus-containing organic compound, and formaldehyde contained in the second part of aqueous formaldehyde solution is 1:0.1 to 0.2:0.7 to 0.9:0.2 to 0.3:0.3 to 0.4 percent, and the mass concentration of the formaldehyde aqueous solution is 37 percent.
3. The preparation method according to claim 1, wherein in the step (1), the mass ratio of phenol, nitrile rubber and p-toluene sulfonic acid is 1:0.02 to 0.03:0.0002 to 0.0003.
4. The method according to claim 1, wherein in the step (1), the process conditions of the first heating and stirring reaction are: stirring and reacting for 1-2 hours at the temperature of 120-130 ℃ at the speed of 300-400 r/min.
5. The preparation method according to claim 1, wherein in the step (1), the first part of the aqueous formaldehyde solution is naturally cooled to the temperature of the second heating and stirring reaction, and is slowly and uniformly added dropwise over 40-50 minutes under the condition of heat preservation.
6. The method according to claim 1, wherein in the step (1), the process conditions of the second heating and stirring reaction are as follows: stirring and reacting for 3-4 hours at the temperature of 95-105 ℃ and the speed of 300-400 r/min.
7. The method according to claim 1, wherein in the step (1), the process conditions of the first vacuum dehydration are: the temperature is 90-100 ℃, the vacuum degree is 8-10 kPa, and the time is 50-60 minutes.
8. The method according to claim 1, wherein in the step (2), the mixture is naturally cooled to a temperature at which the third heating and stirring reaction is carried out;
The process conditions of the third heating and stirring reaction are as follows: stirring and reacting for 90-100 minutes at the temperature of 70-80 ℃ at the speed of 300-400 r/min;
In the step (2), the technological conditions of the second vacuumizing and dehydrating are as follows: the temperature is 80-90 ℃, the vacuum degree is 5-8 kPa, and the time is 100-120 minutes.
9. The preparation method of claim 1, wherein in the step (3), the mass ratio of the phosphorus modified phenolic resin, the absolute ethyl alcohol and the titanate acetylacetone mixture is 2.5-3.5: 2:1.5 to 2, wherein the titanate and acetylacetone mixed solution is prepared by mixing titanate and acetylacetone according to a mass ratio of 1:10, mixing;
and slowly and uniformly adding the titanate acetylacetone mixed solution into the phenolic resin dispersion liquid by 30-40 minutes.
10. The method according to claim 1, wherein in the step (3), the process conditions of the stirring reaction are: stirring and reacting for 50-60 minutes at the temperature of 25-30 ℃ and at the speed of 200-300 r/min;
The process conditions of the reduced pressure concentration are as follows: the temperature is 70-75 ℃, the vacuum degree is 5-8 kPa, and the time is 80-100 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410823467.XA CN118702882A (en) | 2024-06-25 | 2024-06-25 | Preparation method of modified phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410823467.XA CN118702882A (en) | 2024-06-25 | 2024-06-25 | Preparation method of modified phenolic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118702882A true CN118702882A (en) | 2024-09-27 |
Family
ID=92821273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410823467.XA Pending CN118702882A (en) | 2024-06-25 | 2024-06-25 | Preparation method of modified phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118702882A (en) |
-
2024
- 2024-06-25 CN CN202410823467.XA patent/CN118702882A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112745469A (en) | Production method of high-temperature-resistant resin | |
| CN107082859A (en) | A kind of preparation method of the heat resistance modified phenolic resin of toughness reinforcing | |
| CN110079049B (en) | Sheet molding compound resin composition, sheet molding compound and preparation method thereof | |
| CN112175198A (en) | Novel reactive lignin-based flame retardant and preparation method and application thereof | |
| CN115386066A (en) | High-performance bio-based thermosetting epoxy resin and preparation method thereof | |
| CN118702882A (en) | Preparation method of modified phenolic resin | |
| CN111777744B (en) | Halogen-free flame-retardant epoxy resin precursor, molding compound product, preparation method and application thereof | |
| CN111748205B (en) | High-temperature-resistant wave-transparent hybrid resin system suitable for wet winding and preparation method thereof | |
| CN116554534B (en) | Environment-friendly polypropylene flame-retardant foam material and preparation process thereof | |
| CN112708087A (en) | Nano silicon dioxide modified water-based phenolic resin and preparation method thereof | |
| CN111825821A (en) | Preparation method of solvent-free phosphorus-containing cardanol-based epoxy curing agent | |
| CN113801431B (en) | High-toughness high-strength phenolic resin material and preparation method thereof | |
| CN105290984A (en) | Inorganic compounded abrasive resin grinding wheel and preparation method thereof | |
| CN115073785A (en) | Phthalonitrile resin film and preparation method thereof | |
| CN111087562A (en) | Preparation method of blending modified phenolic resin | |
| CN107446097B (en) | Preparation method of high-temperature-resistant phenolic resin with organic silicon resin as curing agent | |
| CN110951252A (en) | Novel cyanate/epoxy modified resin matrix composition | |
| CN114656376A (en) | Method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting bisphenol method | |
| CN111303361A (en) | Special phenolic resin for environment-friendly high-strength precoated sand | |
| CN108219092B (en) | Preparation method of benzoxazine resin | |
| CN118440638B (en) | Resin for hot melt adhesive film process and preparation method thereof, and hot melt adhesive film preparation method and application thereof | |
| CN111499818B (en) | Method for preparing thermoplastic boron phenolic resin by solid-phase synthesis method | |
| CN113024776B (en) | Heat-sensitive epoxy curing agent, preparation method thereof and epoxy resin composition | |
| CN107556749B (en) | Coordination and anion synergistic catalytic curing cyanate ester resin system and preparation method thereof | |
| CN116217847A (en) | High-temperature-resistant modified phenolic resin for commutator and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |